Process for preparing substituted bis-ethers

Abstract

Substituted bis-ethers, such as α,107 -bis-(4-aminophenoxy)-alkyls, are prepared in process which involves sequential addition of reactants, reagents or neutralizing compounds without recovery of intermediate products such as diamides and diamine acid salts. When water is used as the solvent, the process is simplified and product yields in excess of about 70% are obtained.

What is claimed: 
     
       1. An aqueous process for preparing a water insoluble substituted bis-ether of the formula ##STR4## wherein R is a divalent alkyl radical having from about 2 to about 40 carbon atoms, a divalent cycloalkyl radical having from about 3 to about 8 carbon atoms, a divalent bridged ring aliphatic radical having from about 5 to about 10 carbon atoms, a divalent aromatic radical, a divalent alkylaryl radical having from about 7 to about 30 carbon atoms or a divalent fused ring aromatic compound having from about 10 to about 14 carbon atoms; Y is a monovalent radical selected from the group consisting of an amino radical, a halogen radical, a hydroxy radical, an alkyl radical of 1 to 30 carbon atomS, an aryl radical of 6 to 14 carbon atoms, a cycloalkyl radical having from 3 to 8 carbon atoms, an alkylaryl radical having from 7 to 30 carbon atoms, a substituted alkylaryl radical, a substituted aryl radical or a substituted cycloalkyl radical; and n is an integer of from about 1 to about 5 inclusive, which process comprises: ( a) refluxing an admixture comprising (1) an organic dihalo compound, (2) an aqueous solution of a phenol which is substituted with at least one halogen-reactive moiety, and (3) an aqueous base solution, for a period of time sufficient to form an intermediate compound;   (b) hydrolyzing said intermediate compound with a mineral acid; and   (c) neutralizing said hydrolyzed compound with a base to provide the substituted bis-ether.   
     
     
       2. The process of claim 1 wherein R is a divalent alkyl radical having from about 2 to about 18 carbon atoms. 
     
     
       3. The process of claim 1 wherein R is a divalent alkyl radical having from about 2 to about 10 carbon atoms. 
     
     
       4. The process of claim 2 wherein Y is an amino radical. 
     
     
       5. The process of claim 1 wherein steps (a) and (b) are conducted under an inert gaseous atmosphere. 
     
     
       6. The process of claim 5 wherein the inert gaseous atmosphere is provided by at least one gas selected from the group consisting of nitrogen, argon, helium, neon, krypton, xenon, radon or carbon dioxide. 
     
     
       7. The process of claim 6 wherein the gas is nitrogen. 
     
     
       8. The process of claim 1 wherein the organic dihalo compound is selected from the group consisting of dibromoethane, dibromopropane, dibromobutane, dibromopentane, dibromohexane, dibromoheptane, dibromooctane, dibromononane, dibromodecane, dichloroethane, dichloropropane, dichlorobutane, dichloropentane, dichlorohexane, dichloroheptane, dichlorooctane, dichlorononane, dichlorodecane, diiodoethane, diiodopropane, diiodobutane, diiodopentane, diiodohexane, diiodoheptane, diiodooctane, diiodononane and diiododecane. 
     
     
       9. The process of claim 1 wherein the organic dihalo compound is a dibromoalkyl compound, the alkyl moiety thereof having from about 2 to about 40 carbon atoms. 
     
     
       10. The process of claim 9 wherein the alkyl moiety has from about 2 to about 10 carbon atoms. 
     
     
       11. The process of claim 1 wherein the phenol is also substituted with at least one monovalent group selected from the group consisting of alkyl radicals having from 1 to 40 carbon atoms, aryl radicals having 6 to 14 carbon atoms, cycloalkyl radicals having from 3 to 8 carbon atoms, alkylaryl radicals having from 7 to 30 carbon atoms, substituted alkylaryl radicals, substituted aryl radicals, substituted cycloalkyl radicals, ether radicals, imido radicals and amido radicals. 
     
     
       12. The process of claim 11 wherein the monovalent group is an alkyl radical having from 1 to 12 carbon atoms or an aryl radical having from 6 to 10 carbon atoms. 
     
     
       13. An aqueous process for preparing a water-insoluble diamine of the formula ##STR5## wherein R is a divalent alkyl radical having from about 2 to about 40 carbon atoms, a divalent cycloalkyl radical having from about 3 to about 8 carbon atoms, a divalent bridged ring aliphatic radical having from about 5 to about 10 carbon atoms, a divalent aromatic radical, a divalent alkylaryl radical having from about 7 to about 30 carbon atoms or a divalent fused ring aromatic compound having from about 10 to about 14 carbon atoms which comprises, (a) refluxing an admixture comprising (1) an organic dihalo compound, (2) an aqueous solution of an amidophenol, and (3) an aqueous base solution for a period of time sufficient to form an aqueous dispersion of a bis-(4-amidophenoxy)-R compound;   (b) hydrolyzing the aqueous dispersion with a mineral acid to convert the bis-(4-amidophenoxy)-R compound to its corresponding diamine acid salt; and   (c) contacting the diamine acid salt solution with sufficient aqueous base solution to convert said diamine acid salt to its corresponding free diamine.   
     
     
       14. The process of claim 13 wherein R is a divalent alkyl radical having from about 1 to about 18 carbon atoms. 
     
     
       15. The process of claim 13 wherein R is a divalent alkyl radical having from about 1 to about 10 carbon atoms. 
     
     
       16. The process of claim 13 wherein the organic dihalo compound is selected from the group consisting of dibromoethane, dibromopropane, dibromobutane, dibromopentane, dibromohexane, dibromoheptane, dibromooctane, dibromononane, dibromodecane, dichloroethane, dichloropropane, dichlorobutane, dichloropentane, dichlorohexane, dichloroheptane, dichlorooctane, dichlorononane, dichlorodecane, diiodoethane, diiodopropane, diiodobutane, diiodopentane, diiodohexane, diiodoheptane, diiodooctane, diiodononane and diiododecane. 
     
     
       17. The prooess of claim 13 wherein the organic dihalo compound is a dibromoalkyl oompound, the alkyl moiety thereof having up to about 40 carbon atoms. 
     
     
       18. The process of claim 17 wherein the alkyl moiety has from about 1 to about 10 carbon atoms. 
     
     
       19. The process of claim 13 wherein the amidophenol is also substituted with at least one monovalent group selected from the group consisting of alkyl radicals having from 1 to 40 carbon atoms, aryl radicals having 6 to 14 carbon atoms, cycloalkyl radicals having from 3 to 8 carbon atoms, alkylaryl radicals having from 7 to 30 carbon atoms, substituted alkylaryl radicals, substituted aryl radicals, substituted cycloalkyl radicals, ether radicals, imido radicals and amido radicals. 
     
     
       20. The process of claim 19 wherein the monovalent group is an alkyl radical having from 1 to 12 carbon atoms or an aryl radical having from 6 to 10 carbon atoms. 
     
     
       21. The process of claim 13 wherein steps (a) and (b) are conducted under an inert gaseous atmosphere. 
     
     
       22. The process of claim 21 wherein the inert gaseous atmosphere is provided by at least one gas selected from the group consisting of nitrogen, argon, helium, neon, krypton, xenon, radon or carbon dioxide. 
     
     
       23. The process of claim 22 wherein the gas is nitrogen.